KR20060002984A - Electrolyte composition and cell - Google Patents

Abstract

An electrolyte composition characterized by comprising: (1) a polymer having an ether bond as an optional ingredient; (2) an additive comprising an ether compound having ethylene oxide units as an optional ingredient; (3) a lithium salt compound; and (4) a cyclic carbonate having an unsaturated group. The electrolyte composition is excellent in processability, moldability, mechanical strength, flexibility, heat resistance, etc. and has significantly improved electrochemical properties with respect to action on lithium metal.

Description

ELECTROLYTE COMPOSITION AND CELL

The present invention relates to an electrolyte composition containing a lithium salt compound and a cyclic carbonate having an unsaturated group, and more particularly, to an electrolyte composition suitable as a material for electrochemical devices such as batteries, capacitors, and sensors.

Conventionally, as the electrolyte constituting an electrochemical device such as a battery, a capacitor, a sensor, and the like, a polymer electrolyte containing an electrolyte solution or an electrolyte solution in the form of a gel is used in terms of ion conductivity, which may cause damage to the device due to leakage of the electrolyte solution, In addition, a problem has been pointed out such that an electrolytic solution reacts with a positive electrode or a negative electrode, and the electrochemical properties thereof are lowered. In contrast, solid electrolytes such as inorganic crystalline materials, inorganic glass, and organic high molecular materials have been proposed. Organic polymer-based materials are generally excellent in workability and formability, and progress is expected in view of the fact that the resulting solid electrolyte has flexibility and bending workability and the design freedom of the device to be applied is increased. However, the present situation is inferior to other materials in terms of ion conductivity.

Through the discovery of ionic conductivity in homopolymers and alkali metal ion systems of ethylene oxide, research into polymer solid electrolytes has been actively conducted. As a result, the polymer matrix is considered to be the most promising polyether such as polyethylene oxide in view of its high mobility and solubility of metal cations. The movement of ions is expected to occur in the amorphous part, not in the crystalline part of the polymer. Since then, copolymerization with various epoxides has been performed in order to reduce the crystallinity of polyethylene oxide. US Pat. No. 4,818,644 discloses a solid electrolyte consisting of a copolymer of ethylene oxide and methylglycidyl ether. However, not all were satisfactory in ion conductivity.

For this reason, although an attempt to apply a specific alkali metal salt to a diethylene glycol methylglycidyl ether-ethylene oxide crosslinked body and apply it to a polymer solid electrolyte is disclosed in Japanese Patent Laid-Open No. 9-324114, practically sufficient conductivity The value is not obtained. In order to further improve this ion conductivity, a polymer solid electrolyte containing an aprotic organic solvent, a derivative of branched polyethylene glycol, or the like is also proposed in WO98 / 07772 including the present applicant. However, these electrolytes react with lithium metal or dendrides precipitate on the surface of lithium metal when lithium metal is used for the electrode, and the electrochemical properties are significantly reduced.

Disclosure of the Invention

(Technical problem to be solved)

It is an object of the present invention to provide an electrolyte composition, in particular a polymer electrolyte, having excellent ion conductivity and electrochemical properties.

(Means to solve the task)

The present invention

 (1) a polymer having an ether bond present as needed;

 (2) an additive consisting of an ether compound having an ethylene oxide unit present as necessary;

 (3) a lithium salt compound,

 (4) cyclic carbonates having unsaturated groups

An electrolyte composition, comprising at least one of the components (1) and (2), is provided.

In addition, the present invention also provides a battery using the electrolyte composition.

When the electrolyte composition of this invention is used, it also discovered that the high performance battery which is stable to lithium metal is obtained.

(Beneficial effect over conventional technology)

The solid electrolyte composition of the present invention is excellent in processability, moldability, mechanical strength, flexibility and heat resistance, and the electrochemical properties of the lithium metal are remarkably improved. Therefore, it can be applied to electronic devices, such as a large capacity battery (especially a secondary battery), a large capacity capacitor, a display element, for example, an electrochromic display.

Preferred Aspects of the Invention

The electrolyte composition of the present invention contains at least one of the polymer (1) and the additive (2). The electrolyte composition may contain both the polymer (1) and the additive (2).

The polymer (1) having an ether bond is a copolymer having a structural unit represented by the following formula (i) and a structural unit represented by the following formula (ii), or a structural unit (i), a structural unit (ii), And it is preferable that it is a copolymer which has a crosslinkable structural unit represented by following formula (iii). Moreover, a random copolymer is preferable.

[Wherein, R ¹ is an alkyl group, a phenyl group or a -CH _² OR _2, R ₂ is an alkyl group or a phenyl group having 1 to 6 carbon atoms or having a carbon number of _{1~6 - (- CH 2 -CH 2} -O-) a - R ^{2 ′} or —CH [CH ₂ —O — (— CH ₂ —CH ₂ —O—) _b —R ^{2 ′} ] ₂ , R ^{2 ′} is an alkyl group having 1 to 6 carbon atoms, and a and b are 0 to Is an integer of 12.]

[Wherein, R ³ represents a reactive group having (a) a reactive silicon group, (b) a methylepoxy group, (c) an ethylenically unsaturated group or (d) a halogen atom]

The monomer which comprises the structural unit (i) in the polymer (1) is ethylene oxide.

The oxirane compound constituting the structural unit (ii) in the polymer (1) includes an alkylene oxide and a glycidyl ether compound which may have a substituent. Specifically, oxirane compounds such as propylene oxide, methylglycidyl ether, butylglycidyl ether, styrene oxide, phenylglycidyl ether, and 1,2-epoxyhexane, ethylene glycol methyl glycidyl ether, and diethylene glycol Methylglycidyl ether, triethylene glycol methylglycidyl ether, 1,3-bis (2-methoxyethoxy) propane2-glycidyl ether, 1,3-bis [2- (2-methoxyether Methoxy) ethoxy] propane 2-glycidyl ether.

The reactive functional group of the oxirane compound forming the crosslinkable structural unit (iii) in the polymer (1) is (a) a reactive silicon group, (b) a methylepoxy group, (c) an ethylenically unsaturated group, or (d) halogen It is an atom.

The oxirane compound having the reactive silicon group (a) includes 2-glycidoxyethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane 3-glycidoxypropyltrimethoxysilane, and 4-glycidoxybutyl Methyltrimethoxysilane, 3- (1,2-epoxy) propyltrimethoxysilane, 4- (1,2-epoxy) butyltrimethoxysilane, 5- (1,2-epoxy) pentyltrimethoxysilane And 1- (3,4-epoxycyclohexyl) methylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. Among them, 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane are particularly preferred.

Examples of oxirane compounds having a methyl epoxy group (b) include 2,3-epoxypropyl-2 ', 3'-epoxy-2'-methylpropyl ether and ethylene glycol-2,3-epoxypropyl-2', 3'-epoxy. -2'-methylpropyl ether, and diethylene glycol-2,3-epoxypropyl-2 ', 3'-epoxy-2'-methylpropyl ether, 2-methyl-1,2,3,4-diepoxybutane , 2-methyl-1,2,4,5-diepoxypentane, 2-methyl-1,2,5,6-diepoxyhexane, hydroquinone-2,3-epoxypropyl-2 ', 3'-epoxy- 2'-methylpropyl ether, catechol-2,3-epoxypropyl-2 ', 3'-epoxy-2'-methylpropyl ether, etc. are mentioned.

Among them, in particular, 2,3-epoxypropyl-2 ', 3'-epoxy-2'-methylpropyl ether, and ethylene glycol-2,3-epoxypropyl-2', 3'-epoxy-2'-methylpropyl ether Is preferred.

Examples of the oxirane compounds having an ethylenically unsaturated group (c) include allylglycidyl ether, 4-vinylcyclohexyl glycidyl ether, α-terpinylglycidyl ether, cyclohexenylmethylglycidyl ether, and p-vinyl Benzylglycidyl ether, allylphenylglycidyl ether, vinylglycidyl ether, 3,4-epoxy-1-butene, 3,4-epoxy-1-pentene, 4,5-epoxy-2-pentene, 1 , 2-epoxy-5,9-cyclododecadiene, 3,4-epoxy-1-vinylcyclohexene, 1,2-epoxy-5-cyclooctene, glycidyl acrylate, glycidyl methacrylate, sorb B-glycidyl, cinnamic acid glycidyl, crotonic acid glycidyl, glycidyl-4-hexenoate are used.

Preferably, allyl glycidyl ether, glycidyl acrylate, and glycidyl methacrylate are mentioned.

Examples of the oxirane compounds having a halogen atom (d) include epibromohydrin, epiiodohydrin, epichlorohydrin and the like.

The polymerization method of the polymer having an ether bond is a polymerization method of obtaining a multi-component copolymer by ring-opening reaction of an ethylene oxide moiety, and is the same as the method described in JP-A-63-154736 and JP-A-62-169823. Is done.

The polymerization reaction can be carried out as follows. As the catalyst for ring-opening polymerization, a catalyst system mainly composed of organic aluminum, a catalyst system mainly composed of organic zinc, an organic tin-phosphate ester condensate catalyst system, and the like are used, and each monomer is used in the presence or absence of a solvent. A polyether copolymer is obtained by making it react at 80 degreeC and stirring. Among them, the organic tin-phosphate ester condensate catalyst system is particularly preferable in view of the degree of polymerization or the properties of the copolymer to be produced. In a polymerization reaction, the reactive functional group does not react, and the polymer (1) which has a reactive functional group is obtained.

With respect to the polymer (1) having an ether bond used in the electrolyte composition of the present invention, the proportion of ethylene oxide constituting the structural unit (i) is 10 to 95% by weight, preferably 20 to 90% by weight, and the structural unit ( The amount of the oxirane compound constituting ii) is 90 to 5% by weight, preferably 80 to 10% by weight, and the oxirane compound constituting the crosslinkable structural unit (iii) is 0 to 30% by weight, preferably 0 to 20% by weight, in particular 0.1-20% by weight.

When the amount of the oxirane compound constituting the crosslinkable structural unit (iii) is 30% by weight or less, the crosslinked polymer has good ionic conductivity.

In the case where the amount of ethylene oxide constituting the structural unit (i) is 10% by weight or more, the lithium salt compound is easy to melt even at low temperatures, and thus has high ion conductivity.

In general, it is known that the ion conductivity is improved by lowering the glass transition temperature. However, in the polymer electrolyte composition of the present invention, it was found that the effect of improving the ion conductivity is remarkably large.

The molecular weight of the polymer used in the polymer electrolyte composition is preferably within the range of the weight average molecular weight of 10 ⁴ to 10 ⁸ , preferably within the range of 10 ⁵ to 10 ⁷ in order to obtain good processability, moldability, mechanical strength and flexibility. .

As a crosslinking method of the polymer (1) whose reactive functional group is a reactive silicon group (a), it can bridge | crosslink by reaction of a reactive silicon group and water. In order to increase the reactivity, tin compounds such as dibutyltin dilaurate and dibutyltin maleate, titanium compounds such as techlabutyl titanate and tetrapropyl titanate, aluminum trisacetylacetonate and aluminum trisethylacetoacetate You may use organometallic compounds, such as aluminum compounds, such as these, or amine compounds, such as butylamine and octylamine, as a catalyst.

Polyamines, acid anhydrides, etc. are used in the crosslinking method of the polymer (1) whose reactive functional group is a methyl epoxy group (b).

 Examples of the polyamines include aliphatic polyamines such as diethylenetriamine and dipropylenetriamine, aromatic polyamines such as 4,4'-diaminodiphenyl ether, diaminodiphenyl sulfone, m-phenylenediamine and xylylenediamine. Can be. The amount of the polyamine added varies depending on the type of polyamine, but is usually in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the polymer electrolyte composition excluding the plasticizer (ie, additive (2)).

Examples of the acid anhydrides include maleic anhydride, phthalic anhydride, methylhexahydrophthalic anhydride, tetramethylene maleic anhydride, tetrahydrophthalic anhydride and the like. Although the addition amount of an acid anhydride changes with kinds of acid anhydride, it is the range of 0.1-10 weight part normally with respect to 100 weight part of polymer electrolyte compositions except a plasticizer. An accelerator may be used for these crosslinking, and phenol, cresol, resorcin, etc. may be used for the crosslinking reaction of polyamines, and benzyldimethylamine, 2- (dimethylaminoethyl) phenol, dimethylaniline, etc. have. The amount of the accelerator added varies depending on the accelerator, but is usually in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the crosslinking agent.

As a crosslinking method of the polymer (1) whose reactive functional group is an ethylenically unsaturated group (c), active energy rays, such as a radical initiator selected from an organic peroxide, an azo compound, etc., an ultraviolet-ray, an electron beam, are used. Moreover, the crosslinking agent which has silicon hydride can also be used.

As the organic peroxide, those commonly used for crosslinking applications such as ketone peroxide, peroxy ketal, hydroperoxide, dialkyl peroxide, diacyl peroxide and peroxy ester are used, and 1,1-bis (t-butylperoxy) is used. -3,3,5-trimethylcyclohexane, di-t-butylperoxide, t-butylcumylperoxide, dicumylperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, Benzoyl peroxide, and the like. Although the addition amount of an organic peroxide changes with kinds of organic peroxide, Usually, it exists in the range of 0.1-10 weight part with respect to 100 weight part of polymer electrolyte compositions except a plasticizer.

As an azo compound, what is normally used for crosslinking uses, such as an azonitrile compound, an azoamide compound, and an azoamidine compound, can be used, A 2,2'- azobisisobutyronitrile, 2,2'- azobis (2- Methylbutyronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2-azobis (2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2 , 2'-azobis (2-methylpropane), 2,2'-azobis [2- (hydroxymethyl) propionitrile] and the like. Although the addition amount of an azo compound changes with kinds of azo compounds, it is normally in the range of 0.1-10 weight part with respect to 100 weight part of polymer electrolyte compositions except a plasticizer.

In crosslinking by active energy ray irradiation such as ultraviolet rays, glycidyl acrylate, glycidyl methacrylate, and glycidyl ether cinnamic acid are particularly preferable. Moreover, benzoin ethers, such as acetophenones, such as diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl propane- 1-one, and phenyl ketone, benzoin, benzoin methyl ether, as a sensitizing auxiliary agent, Benzophenones such as benzophenone and 4-phenylbenzophenone, thioxanthones such as 2-isopropyl thioxanthone and 2,4-dimethyl thioxanthone, 3-sulfonyl azide benzoic acid, 4-sulfonyl azide benzoic acid and the like Azides and the like can be used arbitrarily.

Ethylene glycol diacrylate, ethylene glycol dimethacrylate, oligoethylene glycol diacrylate, oligoethylene glycol dimethacrylate, allyl methacrylate, allyl acrylate, diallyl maleate, triallyl isocyanur as crosslinking aids Elate, bisphenyl maleimide, maleic anhydride, etc. can be used arbitrarily.

As a compound which has silicon hydride which crosslinks an ethylenically unsaturated group (c), the compound which has at least 2 silicon hydride is used. In particular, a polysiloxane compound or a polysilane compound is preferable.

Examples of the catalyst of the hydrosilylation reaction include transition metals such as palladium and platinum, compounds thereof, and complexes. Peroxides, amines and phosphines are also used. The most common catalysts include dichlorobis (acetonitrile) palladium (II), chlorotris (triphenylphosphine) rhodium (I) and chloroplatinic acid.

As a crosslinking method of the polymer (1) which has an ether bond whose reactive functional group is a halogen atom (d), crosslinking agents, such as polyamine, mercaptoimidazoline, mercaptopyrimidines, thiourea, and polymercaptan, are used. do. Examples of the polyamines include triethylenetetramine, hexamethylenediamine, and the like. As mercaptoimidazoline, 2-mercaptoimidazoline, 4-methyl-2- mercaptoimidazoline, etc. are mentioned. Examples of mercaptopyrimidines include 2-mercaptopyrimidine, 4,6-dimethyl-2-mercaptopyrimidine, and the like. Examples of thioureas include ethylene thiourea, dibutyl thiourea, and the like. Examples of the polymercaptans include 2-dibutylamino-4,6-dimethylcapto-s-triazine, 2-phenylamino-4,6-dimercaptotriazine and the like. Although the addition amount of a crosslinking agent changes with kinds of crosslinking agent, it is the range of 0.1-30 weight part normally with respect to 100 weight part of polymer electrolyte compositions except a plasticizer.

In addition, the addition of a metal compound serving as a hydroxyl agent to the polymer solid electrolyte is effective in view of the thermal stability of the halogen-containing polymer. Examples of the metal oxide to be used as an oxidizing agent include oxides, hydroxides, carbonates, carboxylates, silicates, borates, phosphates of the periodic table Group II metals, oxides of the Group VIa metals of the periodic table, basic carbonates, basic carboxylates, basic phosphites, and basic Sulfite, tribasic sulfate, and the like. Specific examples include magnesia, magnesium hydroxide, magnesium carbonate, calcium silicate, calcium stearate, triad tetraoxide, tin stearate, and the like. Although the compounding quantity of the metal compound used as said acid-and-acid-acid agent changes with kinds, Usually, it is the range of 0.1-30 weight part with respect to 100 weight part of polymer electrolyte compositions except a plasticizer.

The additive (2) containing an ether compound having ethylene oxide units functions as a plasticizer. When the additive (2) containing an ether compound having an ethylene oxide unit is added to the polymer electrolyte composition, crystallization of the polymer is suppressed, the glass transition temperature is lowered, and many amorphous forms are formed at low temperatures, thereby increasing the ionic conductivity.

As an example of the additive (2) containing the ether compound which has an ethylene oxide unit, the additive represented by either of following formula (iv)-(vii) is preferable.

[In formula, R <^4> -R <^18> is a C1-C6 alkyl group and c-r is a number of 0-12.]

Although the compounding ratio of the additive (2) is arbitrary, the sum total of the polymer (1) and the additive (2) is 100 weight part.

It is preferable that the lithium salt compound (3) used in this invention is soluble in the polymer (1), the mixture which consists of an additive (2), and cyclic carbonate (4). In the present invention, the following lithium salt compounds are preferably used.

Li-ion of the cation and chloride ion, bromine ion, iodine ion, perchlorate ion, thiocyanate ion, boric acid ion tetrafluoroborate, nitrate _{^{ion, AsF 6 -, PF 6 -}} , stearyl acid ion, octyl acid ion, dodecylbenzenesulfonic acid ion, naphthalenesulfonic acid ion, dodecyl naphthalenesulfonate ion, 7,7,8,8- tetrahydro-dicyano -p- quinolyl nodi methane ^{_{ion, X 1 S0 3 -, [}} (X 1 SO 2) (X ₂ SO ₂ ) N] ^- , [(X ₁ SO ₂ ) (X ₂ SO ₂ ) (X ₃ SO ₂ ) C] ^- , and [(X ₁ SO ₂ ) (X ₂ SO ₂ ) YC] ^- The compound which consists of an anions is mentioned. Provided that X ₁ , X ₂ , X ₃ and Y are electron withdrawing groups. Preferably, X ₁ , X ₂ , and X ₃ are each independently a perfluoroalkyl group or a perfluoroaryl group having 1 to 6 carbon atoms, and Y is a nitro group, nitroso group, carbonyl group, carboxyl group or cyano group . X ₁ , X ₂ and X ₃ may be the same or different.

In the present invention, the amount of the lithium salt compound (3) used may be 0.1 to 1000 parts by weight, preferably 1 to 500 parts by weight based on 100 parts by weight of the total of the polymer (1) and the additive (2). When this value is 1000 parts by weight or less, the workability, moldability, mechanical strength and flexibility of the obtained solid electrolyte are high, and ion conductivity is also high.

When flame retardancy is necessary when using an electrolyte composition, a flame retardant can be used. As a flame retardant, an effective amount (e.g., selected from halides such as epoxy bromide compounds, tetrabrombisphenol A, chlorinated paraffin, antimony trioxide, antimony pentoxide, aluminum hydroxide, magnesium hydroxide, phosphate esters, polyphosphates, and zinc borate) And 10 parts by weight or less based on 100 parts by weight of the total of the polymer (1) and the additive (2).

In the cyclic carbonate (4) having an unsaturated group, the unsaturated group is generally a carbon-carbon double bond.

In the case of a lithium metal battery, the cyclic carbonate 4 reacts with the metal lithium of the negative electrode to form a stable film, and inhibits the reaction between the electrolyte and the metal lithium and the growth of the dendride.

The cyclic carbonate (4) is preferably vinylene carbonate or a derivative thereof or ethylene carbonate having an unsaturated group.

In this invention, it is preferable that an example of vinylene carbonate or its derivative (s) is a compound represented by following formula (viii-1).

[Wherein, R ¹⁹ and R ²⁰ are hydrogen or an alkyl group having 1 to 6 carbon atoms.]

In this invention, it is preferable that the example of ethylene carbonate which has an unsaturated group is a compound represented by following formula (viii-2).

[Wherein, R ²¹ is H or an alkyl group having 1 to 6 carbon atoms, R ²² is an alkenyl group having 1 to 6 carbon atoms or -CH ₂ OR ^{22 '} , and R ^22' is an alkenyl group having 1 to 6 carbon atoms .]

The usage-amount of the cyclic carbonate 4 is 1-100 weight part with respect to a total of 100 weight part of components (1) and (2), Preferably the range is 5-80 weight part. The optimum amount may be an amount such that the surface of the metal lithium can react with the cyclic carbonate to form a stable film. If excess cyclic carbonate is present in the polymer electrolyte composition, the electrochemical properties are degraded.

The method of containing the cyclic carbonate (4) is not particularly limited when the electrolyte compound composed of the components (1), (2) and (3) is not crosslinked.

However, in the case of crosslinking and using the electrolyte compounds composed of the components (1), (2) and (3), the cyclic carbonate (4) is composed of the electrolyte compounds composed of the components (1), (2) and (3). After crosslinking, it is necessary to impregnate. In the case of crosslinking after containing the cyclic carbonate (4) before the crosslinking of the electrolyte compound composed of the components (1), (2) and (3), the electrochemical properties are not improved. This is considered to be because the ethylenically unsaturated group of the cyclic carbonate 4 is lost by crosslinking.

In the case where the electrolyte compound composed of the components (1), (2) and (3) is used by crosslinking, the method of impregnating the cyclic carbonate (4) is not particularly limited, but the components (1), (2) and (3). Method for impregnating the crosslinked product of the electrolyte compound consisting of directly with the cyclic carbonate (4), impregnating the mixture with the additive (2), impregnating the mixture with the organic solvent, or component (1) And a method of impregnating a mixture of electrolyte compounds composed of (2) and (3).

Although there is no restriction | limiting in particular in the manufacturing method of the polymer electrolyte composition of this invention, what is necessary is just to mix each component mechanically. In the case of the polymer (1) requiring crosslinking, the components are prepared by mechanically mixing the components and then crosslinking, but may be impregnated with the additive for a long time after crosslinking. As means for mechanically mixing, various kneaders, open rolls, extruders and the like can be arbitrarily used.

In the case where the reactive functional group is a reactive silicon group, the amount of water used in the crosslinking reaction is not particularly limited because it is easily generated by moisture in the atmosphere. It may also be crosslinked by passing it through a cold water or hot water bath for a short time or by exposure to a steam atmosphere.

When a reactive functional group is an ethylenically unsaturated group, when a radical initiator is used, a crosslinking reaction will complete | finish in 1 minute-20 hours under the temperature conditions of 10 degreeC-200 degreeC. In addition, when using energy rays, such as an ultraviolet-ray, a sensitizer is generally used. Usually, a crosslinking reaction is complete | finished in 0.1 second-1 hour on 10 degreeC-150 degreeC temperature conditions. In the crosslinking agent which has silicon hydride, a crosslinking reaction is complete | finished in 10 minutes-10 hours under the temperature conditions of 10 degreeC-180 degreeC.

Although the method of mixing a lithium salt compound (3) and an additive (2) with the polymer (1) (namely, a polyether polyone copolymer) is not restrict | limited, An organic solvent can be used as needed. When prepared using an organic solvent, various polar solvents such as tetrahydrofuran, acetone, acetonitrile, dimethylformamide, dimethyl sulfoxide, dioxane, methyl ethyl ketone, methyl isobutyl ketone, and the like are used alone or It can be mixed and used.

The polymer electrolyte composition mentioned in the present invention is excellent in mechanical strength and flexibility, and it is easy to obtain a solid electrolyte having a large area thin film shape using its properties. For example, the production of a battery using the polymer electrolyte composition of the present invention is possible. In this case, as the positive electrode material, lithium-manganese composite oxide, lithium cobalt oxide, vanadium pentoxide, olivine-type iron phosphate, polyacetylene, polypyrene, polyaniline, polyphenylene, polyphenylene sulfide, polyphenylene oxide, polypyrrole, poly Furan, polyazulene and the like. Examples of the negative electrode material include an interlayer compound in which lithium is occluded between layers of graphite or carbon, a lithium metal, a lithium-lead alloy, and the like. In addition, use of a high ion conductivity as a diaphragm of ion electrodes of cations such as alkali metal ions, Cu ions, Ca ions, and Mg ions is also considered. The polymer electrolyte composition of the present invention is particularly preferable as a material for electrochemical devices such as batteries, capacitors and sensors.

Hereinafter, an Example is shown and this invention is demonstrated concretely.

The monomer conversion composition of the polyether copolymer was determined by ¹ H NMR spectrum. The molecular weight of the polyether copolymer was measured by gel permeation chromatography, and the molecular weight was calculated in terms of standard polystyrene. Gel permeation chromatography measurement was carried out by measuring apparatus RID-6A of Shimadzu Corporation, Shodex KD-807, KD-806, KD-806M and KD-803, and solvent dimethylformamide It carried out at 60 degreeC using (DMF). The glass transition temperature uses the DSC 220 made from Seiko Electronics Co., Ltd., and the calorific value of the melting | fusing heat uses the differential scanning calorimeter DSC7 by a Perkin Elma company. In nitrogen atmosphere, in a temperature range of -100-80 degreeC and a temperature increase rate of 10 degreeC / measured in min. In order to measure the conductivity σ, the sample film was vacuum dried at 30 ° C. for 12 hours in advance. Electrical conductivity was measured at 10 degreeC, the film was sandwiched between electrodes made of SUS, and it calculated by the complex impedance method using the alternating current method of the voltage of 30 mV and a frequency range of 10 Hz-10 MHz.

The stability evaluation with lithium metal in a battery system was calculated | required by the lithium precipitation dissolution efficiency test. Nagano Corporation charge-discharge tester BTS-2004W was used for the lithium precipitation dissolution efficiency test. Metal lithium was used for the copper foil and the counter electrode, and a test cell was prepared by sandwiching the polymer electrolyte composition between the positive electrodes. After Li precipitated for 10 hours at a current density of 0.1 mA / cm 2 at room temperature, Li was dissolved to a final voltage of 2.0 V at a current density of 0.1 mA / cm 2. Lithium precipitation dissolution efficiency was calculated | required with the following formula | equation.

Lithium Precipitation Dissolution Efficiency (%) = (Time required for dissolution of nth cycle / Time required for precipitation of nth cycle) × 100

Synthesis Example (Preparation of Catalyst)

10 g of tributyltin chloride and 35 g of tributyl phosphate were added to a three-necked flask equipped with a stirrer, a thermometer, and a distillation apparatus. Material was obtained. This was then used as catalyst for polymerization.

Polymerization Example 1 (Preparation of Polymer)

Nitrogen-substituted the inside of the glass 4-necked flask having a content of 3 L, and as a catalyst, 2 g of the condensation material shown in the preparation example of the catalyst, 100 g of methylglycidyl ether adjusted to 10 ppm or less of water, and 1,000 g of n-hexane as a solvent were used. In addition, 200 g of ethylene oxide was added sequentially, tracking the polymerization rate of methylglycidyl ether by gas chromatography. The polymerization reaction was stopped with methanol. The polymer was removed by decantation, then dried at 40 ° C. for 24 hours at normal pressure, and further dried at 45 ° C. under reduced pressure for 10 hours to obtain 275 g of polymer. The glass transition temperature of this copolymer was -65 degreeC, the weight average molecular weight was 1.1 million, and the heat of fusion was 7 J / g. ¹ in terms of monomer composition analysis result of the copolymer according to the H NMR spectrum of ethylene oxide was 67wt%, 33wt% methyl glycidyl ether.

Polymerization Example 2 (Preparation of Polymer)

Nitrogen-substituted the inside of the glass 4-necked flask having a content of 3L, and as a catalyst, 100 g of propylene oxide, 10 g of methacrylate and 10 g of methacrylate, and a solvent, 1,000 g of hexane was added, and 200 g of ethylene oxide was added sequentially while tracking the polymerization rate of propylene oxide by gas chromatography. The polymerization reaction was stopped with methanol. The polymer was removed by decantation, then dried at 40 ° C. for 24 hours at normal pressure, and further dried at 45 ° C. under reduced pressure for 10 hours to obtain polymer 283 g. The glass transition temperature of this copolymer was -68 degreeC, the weight average molecular weight was 1.7 million, and the heat of fusion was 7 J / g. ¹ in terms of monomer composition analysis result of the copolymer according to the H NMR spectrum was 67wt% ethylene oxide, propylene oxide 30wt%, glycidyl methacrylate 3wt%.

Polymerization Example 3 (Preparation of Polymer)

180 g of oxirane compound (EM) of the formula (ix) of the following formula (ix) adjusted to 2 g of condensation substance shown in the manufacture example of a catalyst, and 10 ppm or less of water as a catalyst by nitrogen-substituting the inside of the glass 4-necked flask of 3 L of contents 20 g of cyl ether and 1,000 g of n-hexane were added as a solvent, and 120 g of ethylene oxide was added sequentially, tracking the polymerization rate of EM by gas chromatography. The polymerization reaction was stopped with methanol. The polymer was removed by decantation, then dried at 40 ° C. for 24 hours at normal pressure, and further dried at 45 ° C. under reduced pressure for 10 hours to obtain 298 g of a polymer. The glass transition temperature of this copolymer was -72 degreeC, the weight average molecular weight was 1.3 million, and the heat of fusion was 3J / g. ¹ in terms of monomer composition analysis result of the copolymer according to the H MNR spectra was a 37wt% ethylene oxide, EM 57wt%, allyl glycidyl ether 6wt%.

Polymerization Example 4 (Preparation of Polymer)

100 g of the oxirane compound (GM) of the following formula (x) which adjusted to 2 g of condensation substance shown by the manufacture example of a catalyst, and 10 ppm or less of water as a catalyst by nitrogen-substituting the inside of the glass 4-necked flask of 3L of contents, and allyl 10 g of glycidyl ether and 1,000 g of n-hexane were added as a solvent, and 120 g of ethylene oxide was added sequentially while tracking the polymerization rate of GM by gas chromatography. The polymerization reaction was stopped with methanol. The polymer was removed by decantation, then dried at 40 ° C. for 24 hours at normal pressure, and further dried at 45 ° C. under reduced pressure for 10 hours to obtain 205 g of a polymer. The glass transition temperature of this copolymer was -74 degreeC, the weight average molecular weight was 1.15 million, and the heat of fusion was 3 J / g. ¹ in terms of monomer composition analysis result of the copolymer according to the H NMR spectrum was 53wt% ethylene oxide, GM 43wt%, allyl glycidyl ether 4wt%.

Example 1

1 g of ethylene oxide / methylglycidyl ether binary copolymer having a weight average molecular weight obtained in Polymerization Example 1 and an ether compound having an ethylene oxide unit of formula (iv-1) below, as a lithium salt compound 0.7 g of lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) was mixed in 50 g of acetonitrile until uniform, mixed on both surfaces of a 20 μm porous membrane, and dried under reduced pressure at 30 ° C. for 12 hours, A 60 µm electrolyte film containing a porous membrane was obtained.

Example 2

1 g of ethylene oxide / propylene oxide / glycidyl methacrylate terpolymer having a weight average molecular weight of 1.7 million obtained in Polymerization Example 2, an additive containing 2 g of an ether compound having an ethylene oxide unit of formula (iv-1), 0.7 g of lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) as a lithium salt compound, 0.015 g of benzoyl peroxide as an initiator, and 0.3 g of ethylene glycol diacrylate as a crosslinking assistant were mixed until uniform in 50 g of acetonitrile. After the application, the coating was uniformly applied to the PET film. Then, it dried under reduced pressure at 30 degreeC for 12 hours, and also heated in 100 degreeC and 3 hours and nitrogen atmosphere, and obtained 50 micrometers electrolyte crosslinked film.

Example 3

1 g of an ethylene oxide / EM / allyglycidyl ether terpolymer having a weight average molecular weight of 1.3 million obtained in the polymerization example 3 and an ether compound containing an ethylene oxide unit having the ethylene oxide unit of formula (vii-1) below, a lithium salt 0.8 g of lithium bis (perfluoroethylsulfonyl) imide (LiBETI) as a compound, 0.015 g of benzoyl peroxide as an initiator, and 0.3 g of ethylene glycol diacrylate as a crosslinking aid were mixed until uniform in 50 g of acetonitrile. Then, it was uniformly applied to the PET film. Then, it dried under reduced pressure at 30 degreeC for 12 hours, and also heated in 100 degreeC and 3 hours and nitrogen atmosphere, and obtained 50 micrometers electrolyte crosslinked film.

Example 4

1 g of an ethylene oxide / GM / allylglycidyl ether terpolymer having a weight average molecular weight obtained in the polymerization example 4, an ether compound having an ethylene oxide unit of formula (vii-1) and a lithium salt 0.8 g of lithium bis (perfluoroethylsulfonyl) imide (LiBETI) as a compound, 0.015 g of benzoyl peroxide as an initiator and 0.3 g of ethylene glycol diacrylate as a crosslinking aid were mixed until uniform in 50 g of acetonitrile. It was apply | coated uniformly to PET film. Then, it dried under reduced pressure at 30 degreeC for 12 hours, and also heated in 100 degreeC and 3 hours and nitrogen atmosphere, and obtained 50 micrometers electrolyte crosslinked film.

Example 5

The average value of the lithium precipitation dissolution efficiency of the electrolyte composition impregnated with 0.02 g of the ether compound having the ethylene oxide unit of formula (iv-1) containing 5 wt% of vinylene carbonate relative to 0.01 g of the electrolyte film of Example 1 was 83. Was%. The results are shown in Table 1.

Example 6

Ethylene oxide units of formula (vii-1) comprising 10 wt% of vinylene carbonate and 1 M of lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) based on 0.01 g of the electrolyte crosslinked film of Example 2 The average value of the lithium precipitation dissolution efficiency of the electrolyte composition impregnated with an ether compound having 0.02 g was 84%. The results are shown in Table 1.

Example 7

The average value of the lithium precipitation dissolution efficiency of the electrolyte composition impregnated with 0.02 g of an ether compound having an ethylene oxide unit of formula (vii-1) containing 20 wt% of vinylene carbonate relative to 0.01 g of the electrolyte crosslinked film of Example 3 was obtained. 92%. The results are shown in Table 1.

Example 8

The average value of the lithium precipitation dissolution efficiency of the electrolyte composition impregnated with 0.02 g of an ether compound having an ethylene oxide unit of formula (vii-1) containing 40 wt% of vinylene carbonate relative to 0.01 g of the electrolyte crosslinked film of Example 3 91%. The results are shown in Table 1.

Example 9

The average value of the lithium precipitation dissolution efficiency of the electrolyte composition impregnated with 0.02 g of an ether compound having an ethylene oxide unit of formula (vii-1) containing 60 wt% of vinylene carbonate relative to 0.01 g of the electrolyte crosslinked film of Example 4 91%. The results are shown in Table 1.

Comparative Example 1

The average value of the lithium precipitation dissolution efficiency of the electrolyte composition impregnated with 0.02 g of the ether compound having the ethylene oxide unit of formula (vii-1) containing no vinylene carbonate relative to 0.01 g of the electrolyte film of Example 2 was 62%. . The results are shown in Table 1.

Comparative Example 2

1 g of an ethylene oxide / EM / allylglycidyl ether terpolymer having a weight average molecular weight of 1.3 million obtained in the polymerization example 3 and an ether compound having an ethylene oxide unit of the formula (iv-1), a lithium salt 0.7 g of lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) as a compound, 0.015 g of benzoyl peroxide as an initiator, 0.3 g of ethylene glycol diacrylate as a crosslinking aid and 20 wt% of vinylene carbonate to an electrolyte are acetonitrile After mixing until uniform in 50g, it was evenly applied to the PET film. Then, it dried under reduced pressure at 30 degreeC for 12 hours, and also heated in 100 degreeC and 3 hours and nitrogen atmosphere, and obtained 50 micrometers electrolyte crosslinking composition. The average value of the lithium precipitation efficiency of this electrolyte crosslinking composition was 60%. The results are shown in Table 1.

Comparative Example 3

1 g of an ethylene oxide / GM / allylglycidyl ether terpolymer having a weight average molecular weight obtained in the polymerization example 4, an ether compound having an ethylene oxide unit of formula (vii-1) and a lithium salt 0.8 g of lithium bis (perfluoroethylsulfonyl) imide (LiBETI) as a compound, 0.015 g of benzoyl peroxide as an initiator, 0.3 g of ethylene glycol diacrylate as a crosslinking aid and 50 wt% of vinylene carbonate to an electrolyte After mixing until uniform in 50g, it was evenly applied to the PET film. Then, it dried under reduced pressure at 30 degreeC for 12 hours, and also heated in 100 degreeC and 3 hours and nitrogen atmosphere, and obtained the 55 micrometers electrolyte crosslinked film. The average value of the lithium precipitation efficiency of this electrolyte crosslinking composition was 67%. The results are shown in Table 1.

Comparative Example 4

The average value of the lithium deposition efficiency of the electrolyte composition impregnated with 0.02 g of an ether compound having an ethylene oxide unit of formula (vii-1) containing 120 wt% of vinylene carbonate relative to 0.01 g of the electrolyte crosslinked film of Example 2 was 71 Was%. The results are shown in Table 1.

Vinylene carbonate added amount (wt%) Lithium precipitation dissolution efficiency Initial value (%) Peak (%) Average value (%) Example 5 Example 6 Example 7 Example 8 Example 9 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 5 10 20 40 60 0 20 50 120 80 83 91 90 90 46 49 50 36 85 86 93 93 92 65 63 71 79 83 84 92 91 91 62 60 67 71

The average value was obtained by averaging the values of lithium precipitation dissolution efficiency up to the 20th cycle.

Example 10

Example 6 The electrolyte composition obtained, a lithium metal foil, and the positive electrode active material as a negative electrode using lithium cobalt oxide (LiCoO ₂₎ was composed of the secondary battery.

Lithium cobalt acid was prepared by mixing a predetermined amount of lithium carbonate and cobalt carbonate powder and baking at 900 ° C for 5 hours. Next, 5 parts by weight of acetylene black, 10 parts by weight of the polymer obtained in Polymerization Example 2, and 5 parts by weight of lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) were added to 85 parts by weight of the obtained lithium cobaltate. After mixing with a roll, it press-molded at the pressure of 30 Mpa, and it was set as the positive electrode of the battery.

The electrolyte composition obtained in Example 6 was sandwiched between the lithium metal foil and the positive electrode plate, and the charge and discharge characteristics of the battery were examined at room temperature while applying a pressure of 1 MPa so that the interface was in close contact. Charging was performed at a constant current constant voltage up to 4.2 V, and discharge was performed at a constant current. The discharge current was 0.1 mA / cm 2, and charging was performed at 0.1 mA / cm 2. The discharge capacity after 100 cycles of charge and discharge represented 90% of the initial capacity.

Example 11

The secondary battery was produced using the electrolyte composition obtained in Example 7, the lithium metal foil as a negative electrode, and the positive electrode produced in Example 10, and similarly the charge / discharge characteristic was investigated. The discharge capacity after 100 cycles of charge and discharge represented 91% of the initial capacity.

Comparative Example 5

The secondary battery was produced using the electrolyte composition obtained by the comparative example 1, the lithium metal foil as a negative electrode, and the positive electrode produced in Example 10, and similarly the charge / discharge characteristic was investigated. The discharge capacity after 100 cycles of charge and discharge represented 80% of the initial capacity.

Comparative Example 6

The secondary battery was produced using the electrolyte composition obtained by the comparative example 3, the lithium metal foil as a negative electrode, and the positive electrode produced in Example 10, and similarly the charge / discharge characteristic was investigated. The discharge capacity after 100 cycles of charge and discharge represented 78% of the initial capacity.

Example 12

0.004 g (3 wt%) of vinylene carbonate, 0.116 g (97 wt%) of an ether compound having an ethylene oxide unit of formula (iv-1), and 0.08 g of lithium bis (perfluoroethylsulfonyl) imide (LiBETI) The average value of the lithium precipitation dissolution efficiency of the electrolyte containing was 86%. The results are shown in Table 2.

Example 13

0.006 g (5 wt%) of vinylene carbonate and 0.114 g (95 wt%) of an ether compound having an ethylene oxide unit of the formula (iv-1) were used, except that the average value of the lithium precipitation dissolution efficiency of the same electrolyte as in Example 12 was used. Was 91%. The results are shown in Table 2.

Example 14

0.012 g (10 wt%) of vinylene carbonate and 0.108 g (90 wt%) of an ether compound having an ethylene oxide unit of formula (iv-1) were used, except that the average value of the lithium precipitation dissolution efficiency of the same electrolyte as in Example 12 was used. Was 92%. The results are shown in Table 2.

Example 15

0.014 g (10 wt%) of vinylene carbonate, 0.126 g (90 wt%) of an ether compound having an ethylene oxide unit of formula (vii-1), and 0.06 g of lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) The average value of the lithium precipitation dissolution efficiency of the electrolyte containing was 92%. The results are shown in Table 2.

Example 16

0.024 g (20 wt%) of vinylene carbonate and 0.096 g (80 wt%) of an ether compound having an ethylene oxide unit of formula (vii-1) were used, except that the average value of lithium precipitation dissolution efficiency of the same electrolyte as in Example 12 was used. Was 91%. The results are shown in Table 2.

Example 17

0.060 g (50 wt%) of vinylene carbonate and 0.060 g (50 wt%) of an ether compound having an ethylene oxide unit of the formula (vii-1) were used, except that the average value of the lithium precipitation dissolution efficiency of the same electrolyte as in Example 12 was used. Was 91%. The results are shown in Table 2.

Example 18

0.096 g (80 wt%) of vinylene carbonate and 0.024 g (20 wt%) of an ether compound having an ethylene oxide unit of formula (vii-1) were used, except that the average value of the lithium precipitation dissolution efficiency of the same electrolyte as in Example 12 was used. Was 88%. The results are shown in Table 2.

Comparative Example 7

The average value of the lithium precipitation dissolution efficiency of the ether compound containing 0.12 g of the ether compound having the ethylene oxide unit of formula (iv-1) and 0.08 g of LiBETI was 71%. The results are shown in Table 2.

Comparative Example 8

The average value of the lithium precipitation dissolution efficiency of the electrolyte containing 0.14 g of the ether compound having the ethylene oxide unit of the formula (vii-1) and 0.06 g of LiTFSI was 54%. The results are shown in Table 2.

Vinylene carbonate added amount (wt%) Lithium salt compound Lithium precipitation dissolution efficiency Initial value (%) Peak (%) Average value (%) Example 12 3 LiBETI 82 90 86 Example 13 5 LiBETI 83 92 91 Example 14 10 LiBETI 85 94 92 Example 15 10 LiTFSI 86 94 92 Example 16 20 LiBETI 82 93 91 Example 17 50 LiBETI 83 94 91 Example 18 80 LiBETI 88 95 88 Comparative Example 7 0 LiBETI 67 78 71 Comparative Example 8 0 LiTFSI 55 64 54

The average value was obtained by averaging the values of lithium precipitation dissolution efficiency up to the 20th cycle.

Example 19

The secondary battery was constructed using the porous separator (25 micrometers of E25MMS thickness, 38% of porosity) by the Toene Tapyrus Co., Ltd. which impregnated the electrolyte of Example 13, lithium metal foil as a negative electrode, and lithium cobaltate as a positive electrode active material.

Lithium cobalt acid was prepared by mixing a predetermined amount of lithium carbonate and cobalt carbonate powder and baking at 900 ° C for 5 hours. Next, 4 parts by weight of acetylene black and 6 parts by weight of polyvinylidene fluoride were added to the obtained 90 parts by weight of lithium cobalt acid, mixed with a roll, and press-molded at a pressure of 30 MPa to form a positive electrode of the battery.

The porous separator impregnated with the electrolyte of Example 13 was sandwiched between the lithium metal foil and the positive electrode plate, and the charge and discharge characteristics of the battery were investigated at 25 ° C. while applying a pressure of 1 MPa so that the interface was in close contact. The charging was performed at a constant current constant voltage up to a current density of 0.1 mA / cm 2 and an upper limit of 4.2 V, and the discharge was performed at a constant current having a current density of 0.1 mA / cm 2. The discharge capacity after 100 cycles of charge and discharge represented 86% of the initial capacity.

Example 20

The secondary battery was produced using the porous separator in which the electrolyte of Example 15 was impregnated, the lithium metal foil as a negative electrode, and the positive electrode produced in Example 19, and the charge / discharge characteristic was investigated similarly to Example 19. The discharge capacity after 100 cycles of charge and discharge represented 88% of the initial capacity.

Comparative Example 9

The secondary battery was produced using the porous separator which impregnated the electrolyte of the comparative example 7, the lithium metal foil as a negative electrode, and the positive electrode produced in Example 19, and the charge / discharge characteristic was investigated similarly to Example 19. The discharge capacity after 100 cycles of charge and discharge represented 64% of the initial capacity.

Comparative Example 10

The secondary battery was produced using the porous separator which impregnated the electrolyte of the comparative example 8, the lithium metal foil as a negative electrode, and the positive electrode produced in Example 19, and the charge / discharge characteristic was investigated similarly to Example 19. The discharge capacity after 100 cycles of charge and discharge represented 43% of the initial capacity.

Example 21

1 g of ethylene oxide / methylglycidyl ether binary copolymer having a weight average molecular weight obtained in Polymerization Example 1 and an ether compound having an ethylene oxide unit of formula (iv-1) below, as a lithium salt compound 0.7 g of lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) was mixed in 50 g of acetonitrile until uniform, mixed on both sides of a 20 μm porous membrane, and dried under reduced pressure at 30 ° C. for 12 hours, A 60 µm electrolyte film containing a porous membrane was obtained.

Example 22

1 g of ethylene oxide / propylene oxide / glycidyl methacrylate terpolymer having a weight average molecular weight of 1.7 million obtained in Polymerization Example 2, an additive containing 2 g of an ether compound having an ethylene oxide unit of formula (iv-1), 0.7 g of LiTFSI as a lithium salt compound, 0.015 g of benzoyl peroxide as an initiator, and 0.3 g of ethylene glycol diacrylate as a crosslinking assistant were mixed until uniform in 50 g of acetonitrile, and then uniformly mixed with a polyethylene terephthalate resin (PET) film. Applied. Then, it dried under reduced pressure at 30 degreeC for 12 hours, and also heated in 100 degreeC and 3 hours and nitrogen atmosphere, and obtained 50 micrometers electrolyte crosslinked film.

Example 23

1 g of an ethylene oxide / EM / allyglycidyl ether terpolymer having a weight average molecular weight of 1.3 million obtained in the polymerization example 3 and an ether compound containing an ethylene oxide unit having the ethylene oxide unit of formula (vii-1) below, a lithium salt 0.8 g of lithium bis (perfluoroethylsulfonyl) imide (LiBETI) as a compound, 0.015 g of benzoyl peroxide as an initiator and 0.3 g of ethylene glycol diacrylate as a crosslinking aid were mixed until uniform in 50 g of acetonitrile. It was apply | coated uniformly to PET film. Then, it dried under reduced pressure at 30 degreeC for 12 hours, and also heated in 100 degreeC and 3 hours and nitrogen atmosphere, and obtained 50 micrometers electrolyte crosslinked film.

Example 24

1 g of an ethylene oxide / GM / allylglycidyl ether terpolymer having a weight average molecular weight obtained in the polymerization example 4, an ether compound having an ethylene oxide unit of formula (vii-1) and a lithium salt 0.8 g of LiBETI as a compound, 0.05 g of lithium borofluoride (LiBF ₄ ), 0.015 g of benzoyl peroxide as an initiator, and 0.3 g of ethylene glycol diacrylate as a crosslinking aid were mixed until uniform in 50 g of acetonitrile, and then to the PET film. The coating was applied uniformly. Then, it dried under reduced pressure at 30 degreeC for 12 hours, and also heated in 100 degreeC and 3 hours and nitrogen atmosphere, and obtained 50 micrometers electrolyte crosslinked film.

Example 25

The average value of the lithium precipitation dissolution efficiency of the polymer electrolyte composition impregnated with 0.02 g of the ether compound having the ethylene oxide unit of formula (iv-1) containing 6 wt% of vinyl ethylene carbonate relative to 0.01 g of the electrolyte film of Example 21 75%. The results are shown in Table 3.

Example 26

To 0.01 g of the electrolyte crosslinked film excluding the PET film of Example 22, impregnated with 0.02 g of an ether compound having an ethylene oxide unit of formula (vii-1) containing 12 wt% of vinyl ethylene carbonate and 1 mol / kg of LiTFSI The average value of the lithium precipitation dissolution efficiency of the polymer electrolyte composition was 82%. The results are shown in Table 3.

Example 27

Average value of lithium precipitation dissolution efficiency of a polymer electrolyte composition impregnated with 0.02 g of an ether compound having an ethylene oxide unit of formula (vii-1) containing 18 wt% of vinyl ethylene carbonate relative to 0.01 g of the electrolyte crosslinked film of Example 23. Was 91%. The results are shown in Table 3.

Example 28

Average value of lithium precipitation dissolution efficiency of a polymer electrolyte composition impregnated with 0.02 g of an ether compound having an ethylene oxide unit of formula (vii-1) containing 20 wt% of vinyl ethylene carbonate relative to 0.01 g of the electrolyte crosslinked film of Example 24 Was 93%. The results are shown in Table 3.

Example 29

Average value of lithium precipitation dissolution efficiency of a polymer electrolyte composition impregnated with 0.02 g of an ether compound having an ethylene oxide unit of formula (vii-1) containing 50 wt% of vinyl ethylene carbonate relative to 0.01 g of the electrolyte crosslinked film of Example 24 Was 90%. The results are shown in Table 3.

Comparative Example 11

The average value of the lithium precipitation dissolution efficiency of the polymer electrolyte composition which was impregnated with 0.02 g of the ether compound having the ethylene oxide unit of formula (vii-1) containing no vinyl ethylene carbonate relative to 0.01 g of the electrolyte crosslinked film of Example 22 was 62. Was%. The results are shown in Table 3.

Comparative Example 12

The average value of the lithium precipitation dissolution efficiency of the polymer electrolyte composition impregnated with 0.02 g of the ether compound having the ethylene oxide unit of formula (vii-1) containing 20 wt% of ethylene carbonate relative to 0.01 g of the electrolyte crosslinked film of Example 23 58%. The results are shown in Table 3.

Comparative Example 13

The average value of the lithium precipitation dissolution efficiency of the polymer electrolyte composition impregnated with 0.02 g of an ether compound having an ethylene oxide unit of formula (vii-1) containing 20 wt% of propylene carbonate based on 0.01 g of the electrolyte crosslinked film of Example 23 38%. The results are shown in Table 3.

Comparative Example 14

The average of the lithium precipitation efficiencies of the polymer electrolyte composition impregnated with 0.02 g of the ether compound having the ethylene oxide unit of formula (vii-1) containing 120 wt% of vinyl ethylene carbonate relative to 0.01 g of the electrolyte crosslinked film of Example 22 65%. The results are shown in Table 3.

Vinyl Ethylene Carbonate Addition (wt%) Lithium precipitation dissolution efficiency Initial value (%) Peak (%) Average value (%) Example 25 Example 26 Example 27 Example 28 Example 29 Comparative Example 11 Comparative Example 12 Comparative Example 13 Comparative Example 14 6 12 18 20 50 0 0 0 120 68 80 89 91 88 46 46 26 55 80 84 93 94 92 65 61 58 71 75 82 91 93 90 62 58 38 65

The average value was obtained by averaging the values of lithium precipitation dissolution efficiency up to the 20th cycle.

Example 30

As in Example 26 the polymer electrolyte composition obtained, a lithium metal foil as a negative electrode and a positive electrode active material using a lithium cobalt oxide (LiCo0 ₂₎ formed the secondary battery.

Lithium cobalt acid was prepared by mixing a predetermined amount of lithium carbonate and cobalt carbonate powder and baking at 900 ° C for 5 hours. Next, this was pulverized, and 5 parts by weight of acetylene black, 10 parts by weight of the polymer obtained in Polymerization Example 2, and 5 parts by weight of LiTFSI were added to the obtained 85 parts by weight of lithium cobalt acid, mixed with a roll, and press-molded at a pressure of 30 MPa to give a battery It was set as the positive electrode.

The polymer electrolyte composition obtained in Example 26 was sandwiched between the lithium metal foil and the positive electrode plate, and the charge and discharge characteristics of the battery were examined at room temperature while applying a pressure of 1 MPa so that the interface was in close contact. Charging was performed at a constant current constant voltage up to 4.2 V, and discharge was performed at a constant current. The discharge current was 0.1 mA / cm 2, and charging was performed at 0.1 mA / cm 2. The discharge capacity after 100 cycles of charge and discharge represented 90% of the initial capacity.

Example 31

The secondary battery was produced using the polymer electrolyte composition obtained in Example 28, the lithium metal foil as a negative electrode, and the positive electrode produced in Example 30, and similarly the charge / discharge characteristic was investigated. The discharge capacity after 100 cycles of charge and discharge represented 91% of the initial capacity.

Comparative Example 15

The secondary battery was produced using the polymer electrolyte composition obtained by the comparative example 11, the lithium metal foil as a negative electrode, and the positive electrode produced in Example 30, and similarly the charge / discharge characteristic was investigated. The discharge capacity after 100 cycles of charge and discharge represented 80% of the initial capacity.

Example 32

0.004 g (3 wt%) of vinylethylene carbonate, 0.116 g (97 wt%) of an ether compound having an ethylene oxide unit of formula (iv-2), and 0.08 g of lithium bis (perfluoroethylsulfonyl) imide (LiBETI) The average value of the lithium precipitation dissolution efficiency of the electrolyte containing was 82%. The results are shown in Table 4.

Example 33

0.006 g (5 wt%) of vinyl ethylene carbonate and 0.114 g (95 wt%) of an ether compound having an ethylene oxide unit of formula (iv-2) were used, except that the average value of the lithium precipitation dissolution efficiency of the same electrolyte as in Example 32 was used. Was 88%. The results are shown in Table 4.

Example 34

0.012 g (10 w 7%) of vinyl ethylene carbonate and 0.108 g (90 wt%) of an ether compound having an ethylene oxide unit of the above formula (iv-2) were used, except for the lithium precipitation dissolution efficiency of the same electrolyte as in Example 32. The mean value was 93%. The results are shown in Table 4.

Example 35

0.014 g (10 wt%) of vinyl ethylene carbonate, 0.126 g (90 wt%) of an ether compound having an ethylene oxide unit of formula (vii-1), and 0.054 g of lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) The average value of the lithium precipitation dissolution efficiency of the electrolyte containing 0.001 g of lithium boron fluoride (LiBF ₄ ) was 90%. The results are shown in Table 4.

Example 36

0.024 g (20 wt%) of vinyl ethylene carbonate and 0.096 g (80 wt%) of an ether compound having an ethylene oxide unit of formula (vii-1) were used, except that the average value of the lithium precipitation dissolution efficiency of the same electrolyte as in Example 35 was used. Was 89%. The results are shown in Table 4.

Example 37

0.060 g (50 wt%) of vinyl ethylene carbonate and 0.060 g (50 wt%) of an ether compound having an ethylene oxide unit of formula (vii-1) were used, except that the average value of the lithium precipitation dissolution efficiency of the same electrolyte as in Example 32 was used. Was 92%. The results are shown in Table 4.

Vinyl Ethylene Carbonate Addition (wt%) Lithium Salt Compound (mol / kg) Lithium precipitation dissolution efficiency Initial value (%) Peak (%) Average value (%) Example 32 3 LiBETI = 1.0 80 88 82 Example 33 5 LiBETI = 1.0 82 92 88 Example 34 10 LiBETI = 1.0 87 96 93 Example 35 10 LiTFSI = 1.0 LiBF ₄ = 0.05 84 93 90 Example 36 20 LiTFSI = 1.0 LiBF ₄ = 0.05 82 93 89 Example 37 50 LiBETI = 1.0 85 94 92

The average value was obtained by averaging the values of lithium precipitation dissolution efficiency up to the 20th cycle.

Claims (12)

(1) a polymer having an ether bond present as needed; (2) an additive consisting of an ether compound having an ethylene oxide unit present as necessary; (3) a lithium salt compound, (4) cyclic carbonates having unsaturated groups An electrolyte composition, comprising at least one of the components (1) and (2). The copolymer (1) according to claim 1, wherein the polymer (1) having an ether bond has a structural unit represented by the following formula (i), a structural unit represented by the following formula (ii), and / or a structural unit ( The electrolyte composition which is a copolymer which has i), structural unit (ii), and a crosslinkable structural unit represented by following formula (iii).

[Wherein, R ¹ is an alkyl group, a phenyl group or a -CH _² OR _2, R ₂ is an alkyl group or a phenyl group having 1 to 6 carbon atoms or having a carbon number of _{1~6 - (- CH 2 -CH 2} -O-) a - R ^{2 ′} or —CH [CH ₂ —O — (— CH ₂ —CH ₂ —O—) _b —R ^{2 ′} ] ₂ , R ^{2 ′} is an alkyl group having 1 to 6 carbon atoms, and a and b are 0 to Is an integer of 12.]

[Wherein, R ³ represents a reactive group having (a) a reactive silicon group, (b) a methylepoxy group, (c) an ethylenically unsaturated group or (d) a halogen atom] The electrolyte composition according to claim 1, wherein the additive (2) consisting of an ether compound having an ethylene oxide unit is an additive represented by any one of (iv) to (vii).

[In formula, R <^4> -R <^18> is a C1-C6 alkyl group and c-r is a number of 0-12.] The electrolyte composition according to claim 1, wherein the cyclic carbonate (4) having an unsaturated group is vinylene carbonate or a derivative thereof or ethylene carbonate having an unsaturated group. The electrolyte composition according to claim 4, wherein the vinylene carbonate or its derivative is a compound represented by the following formula (viii-1).

[Wherein, R ¹⁹ and R ²⁰ are hydrogen or an alkyl group having 1 to 6 carbon atoms.] The electrolyte composition according to claim 4, wherein the ethylene carbonate having an unsaturated group is a compound represented by the following formula (viii-2).

[Wherein, R ²¹ is H or an alkyl group having 1 to 6 carbon atoms, R ²² is an alkenyl group having 1 to 6 carbon atoms or -CH ₂ OR ^{22 '} , and R ^22' is an alkenyl group having 1 to 6 carbon atoms .] The content of the cyclic carbonate (4) is 100% by weight in total of (1) an additive comprising a polymer having an ether bond, (2) an ether compound having an ethylene oxide unit, and (3) a lithium salt compound. It is 1-100 weight part with respect to a part, The electrolyte composition characterized by the above-mentioned. The electrolyte composition according to claim 1, wherein the polymer (1) having an ether bond has a weight average molecular weight of 10 ⁴ to 10 ⁸ . The electrolyte composition according to claim 1, wherein the electrolyte composition contains a polymer (1) and is produced by impregnating a crosslinked product consisting of components (1) to (3) with a cyclic carbonate (4). The polymer (1) is crosslinked in the state containing the additive (2) and / or the lithium salt compound (3), or the additive (2) and / or the lithium salt compound (3) is crosslinked. An electrolyte composition that is impregnated with. The battery which consists of an electrolyte composition as described in any one of Claims 1-10, a positive electrode, and a negative electrode. The battery according to claim 11, wherein the negative electrode is lithium metal.